Manufacture of azo dyestuffs



Patented Sept. 1, 1931 res PATENT OFFICE j RAINALD BEIGHTMAN AND PERCYCl-ZOR-LEY, OF BLACKLEY,

MANCHESTER, ENGLAND,

CHESTER, ENGLAN D MANUFACTURE OE AZO DYESTUFFS No Drawing. Originalapplication filed April 16, 1928, Serial No. 270,572, and. in GreatBritain April 22,

1927. Divided and this application filed August 24, 1329.

tetrazotized 4:4-diaminodiphenyl monodior tri-sulphide with twomolecules of suitable end components of which at least one is orcontains an amino naphthol sulphonic acid includingin this termtheN-substitutet derivatives thereof, directly coupled with thediaminodiphenyl sulphide residue. The other coupling component may beany of the known coupling components and either coupling component maycontain an azo group. These dyestuffs are represented by the followinggeneral formula wherein R represents a coupling component,

. of making a certain group of dyestuffs of the broad general classdisclosed in our above-mentioned application, namely that group ofdyestuffs in which salicylic acid is used as a coupling component. Thisgroup of dyestuffs has the following general formula wherein a: is aninteger greaterthan 0 and less than l, R. represents a coupled salicylicacid and R represents a coupled aminonaphthol sulphonic acid, includingin this term the N-substituted derivatives thereof. o have found thatespecially advantageous dyestuffs are produced when the N-substitucut isan acyl or monocyclic group.

The dyestuffs of the present invention are very useful for dyeingregenerated cellulose materials, in even level shades.

Regenerated cellulose materials such as viscose silks are now being usedin ever increasing amounts. These materials are difficultto dye in theeven level shades required in a commercial satisfactory product. Thedyeing of regenerated cellulose materials is prepared by combining atetrazotized 4:41-

Serial No. 388,261.

an important technical and industrial problem which has only beenpartially solved;

The dyestuffs of the present invention offer a means for advancing thesolution of this problem. They produce very excellenteven level shadeson regenerated cellulose material. T

We found that dyestuffs having the abovementioned characteristicstructure may be diammodiphenyl monodior tri-sulphide with one molecularproportion of salicylic acid and one molecular proportion of anaminonaphthol sulphonic acid. This is the process which we set forth andclaim in the present application. These dyestuffs may also be preparedby another method as set forth in the application ofone of'us, RainaldBrightman Serial No. 262,048. In that application there is discloseda'process which comprises combining a diazotized 4-nitro-4-aminodiphenyl sulphide with salicylic acid,

reducing the nitro group of the resultant dyestuft' by means ofsodiumsulphide, diaze otizing the amino body thus obtainedand combiningit with an: aminonaphthol sul phonic acid. The dyestuffs produced bysuch a method are ofthe same general typeas herein disclosed.

The following examples are illustrative of the processes employed in thepresent invention and in no way limit the scope of the invention.

Example 1.-216 parts of azfldiaminodiphenyl sulphide are tetrazotizedwith 138 parts of sodium nitrite and 500 parts of 36 1 per centhydrochloric acid and the solution of tetrazo compoun'dis stirred into asolution of 138 parts of salicylic acid in 40 parts of sodium hydroxideand 400 parts of sodium carbonate. The mixture is stirred until couplingis complete when a solution of 387 parts of the sodium salt ofQ-phenylamin 8-naphthol- 6-sulphonic acid is added. Stirring'iscontinued until combination is complete, when the mixture is heated upand the dyestuff isolated by the addition of common salt. It forms adark powder which is soluble in suland in water to brown solutions, andwhich phuric acid to violet-blue colored solutions, 3

. let-grey colored dyes viscose silk a brown shade and wool in brownshades, fast to milling. It is identical with the dyestuffs preparedfrom 4-nitro-4- aminodiphenyl sulphide as described in Example 5 of ourco-p'ending application Serial No. 262,048. If in place of the.Z-phenylainino-8-naphthol-6-sulphonic acid in the above example, we usea solution of 239 parts of 2amino-8-naphthol-6-sulphonic acid, we obtaina dyestufi' giving red-brown dyeings on viscose silk.

Example 2.-To a solution of 138 parts of salicylic acid in 40 parts ofsodium hydroxide and 400 parts of sodium carbonate there is added thetetrazo solution obtained from 216 parts of l:48-diaminodiphenylsulphide and 188 parts of sodium nitrite in the usual way. The mixtureis kept cold and stirred until coupling is complete when there is addeda neutral solution of 'tllQtlmlnOdZO compound obtained by combining 138parts ofdiazotized p-nitroaniline with 319 parts of 1-amino-8- naphthol-ii 6 -disulphonic acid in mineral acid solution inthe known way. Themix;

ture is maintained alkaline and stirred until coupling is complete whenit is heated and thedyestuff isolated by the addition of common salt. Itforms a dark lustrous powder which issol ble in sulphuric acid to dullviogreen solutions. It dyes viscose silk a dark green shade. If in placeof 216 parts of a l-diaminodiphenyl sulphide there are used 280 parts of4;:lf-diamiiiodiphenyl trisulphide, we obtain a dyestuffgiving brightbluish-green shades on viscose silk.

Emmpz 3.280. parts of dze diaminodiphenyl tr is ilphide are tetrazotiaed in the presence of ice nitrite and 500 partsof 36 per centhydrochloric acid. The tetrazo-compound partly separates and the yellowsuspension is run intoa solution of 138 parts of salicylic acid in40parts of sodium hydroxide and lQO parts of sodium carbonate. Afterstirring until i couplingiscompletethere isadded a neutral solution 015239, parts, of 2-amino;5-naphthol= 7-sulphonic ac1d. The mixture isstirred.

until: couplingiscomplete when it is heated upand the dyestuffprecipitated by the addition of common salt. It forms a reddishbrownpowder which is soluble in sulphuric acid to violet colored solutions,and in water to orange-red solutions. It dyes viscose silk an orangeshade.

Emample /,L.216 parts. of 4= :4=.-diaminodiphenyl sulphide aretetrazotized and combinedwith138parts of salicylic acid in alkaline(sodium carbonate) solution. After stirring about halfan hour a solutioncontaining 315.. parts of 2-phenylamino-5-naphthol-7 -s ulphonic acid isadded and the mixture maintained alkaline and stirred until coupling iscomplete. Itis then heated up and the dyestuff isolated by the additionof solutions, and in water to with 1'38fparts of sodium common salt. Itforms a reddish-brown powder giving a violet-blue colored solution inconcentrated sulphuric acid, turning red der and ultimately affording areddish-brown precipitate on dilution, and soluble in water to a brownsolution substantially unchanged on addition of alkali and yielding areddishbrown precipitate on addition of mineral acids. It dyes viscosesilk a red shade.

In the following table We set forth further examples of dyestuffs of thebroad gen eral class to which our present invention relates. In the lastcolumn of this table there is set forth the shade on viscose silk pro--duced by these dyestuffs.

First cou- Second coupling com- Shade on Dlamme 1x5 58? ponent viscosesilk 4: 4 diamino di- Salicylic Z-acetamino 8 napli- Scarlet.

phcnyl monosulacid. thol-G-sulphonic acid. ph.ide. ditto ditto 2-amino 8naphtholditto.

6 sulphonic acid (acid coupled).

4: 4 diamino di- Salicylic 2 amino 8 napthol- Re (1 di Sllphenyl.tllSlllacid. (i-sulplionic acid. brown. pliide.

ditto ditto 2-acetamino 8 naph- Ycllowish thol 6 sulphonic red. acid.ditto (l1tt0 2 m xylylamino 8 Brown.

naplithol 6 sulphonic acid.

What we claim and desire to secure by Letters Patent is:

1. In. the manufactureof new a-Zodyes. the process which comprisestetrazotizing a diainine of the formula wherein m is an integer greaterthan 0 and less than 4, and coupling the tetrazo compound so producedwith one molecular proportion of'salicylic acid and oneiiiolecularproportion of an aininonaphthol sulphonic acid.

2. In the manufacture of new azo dyes the process which comprisestetrazotizing a diamine of the formula.

wherein m is an integer greater than 0 and lessthan a, and coupling thetetrazo compound so produced with one molecular proportion of salicylicacid and one molecular proportion of an aininonaphthol sulphonic acid ofthe type on sona- NHR3 1 or- @NHIQ H noas wherein represents hydrogen,an acyl group ora monocyclic group.

3. In the-manufactureof new azo dyes,

the process which comprises tetrazotizing a diamine of the formula andcoupling the tetrazo compound so produced with one molecular proportionof sali cylic acid and one molecular proportion of an aminonaphtholsulphonic acid.

4. In the manufacture of new azo dyes, the process which comprisestetrazotizing a diamine of the formula and coupling the tetrazo compoundso produced with one molecular proportion of sali- I cylic acid and onemolecular proportion of an aminonaphthol sulphomc ac1d of the H S O HNHRa I or NHRa O H H038 wherein R represents hydrogen, an acyl group, ora monocyclic aryl group.

5. In the manufacture of new azo dyes, the

process which comprises tetrazotizing a di-* amine of the formula andcoupling the tetrazo compound so produced with one molecular proportionof salicylic ac1d and one molecular proportion of an ammonaphtholsulphonic ac1d of the type NHR HOaS

wherein R represents hydrogen, an acyl group, or a monocyclic arylgroup.

6. In the manufacture of new azo dyes, the process which comprisestetrazotizing a diamlne of the formula and coupling the tetrazo compoundso pro duced with one molecular proportion of salicylic acid and onemolecular proportion of a 2 :S-aminonaphthol sulphonic acid of the typeNHRs wherein R represents a monocyclic aryl group.

7. In the manufacture of new azo dyes, the

process which comprises tetrazotizing a diamine of the formula andcoupling the tetrazo compound so produced with one molecular proportionof salicylic acid and one molecular proportion of2-phenylamino-8-naphthol-6-sulphonic acid.

8. New aZo dyes having the probable general formula wherein a: is aninteger greater than 0 and less than 4, R represents a coupled salicylicacid and R represents a coupled aminonaphthol sulphonic acid of the typeon s 0 3H NHRa I or NHR3 H H 0 3S wherein R represents hydrogen, an acylgroup,'or a monocyclic aryl gro p. 10. New azo dyes having the probablegen- 'eral formula wherein It represents a coupled salicylic acid and Rrepresents a coupled aminonapht'hol sulphonic acid, the said dyes beingsoluble in concentrated sulphuric acid and in water and dyeing viscosesill-r in even level shades.

11. New azo dyes having the probable general formula wherein Rrepresents a coupled salicylic acid and R represents a coupledaminonaphthol sulphonic acid of the type wherein R represents hydrogen,an acyl group or monocyclic aryl group, the said dyes being soluble inconcentrated sulphuric acid and in water and dyeing viscose silk in evenlevel shades.

12. New azo dyes having the probable general formula wherein Rrepresents a coupled salicylic acid and R represents a coupledaminonaphthol sulphonic acid of the type NHR:

wherein R represents hydrogen, anacyl group or a menocyclic aryl group,said dyes being soluble in concentrated sulphuric acid and in water anddyeing viscose silk in even level shades.

13. New azo dyes having the probable general formula wherein Rrepresents a coupled salicylic acid and R represents coupled 2S-annnonaphthol sulpnonic acld of tne type NHRs wherein R represents amonocyclie aryl group, the. said dyes being soluble in concentratedsulphuric acid and in water and dyeing viscose silk in even levelshades.

14. New azo dye having the formula and coupling the tetrazo compound soformed with one molecular proportion of salicylic acid and onemolecular. proportion of an aminonaphthol sulphonic acid of the typeH033 NHR wherein R represents hydrogen, an acyl group or a monocyclicaryl group 16. New azo dyes having the probable formula wherein Rrepresents a coupled salicylic acid and R represents a coupledaminonaphthol sulphonic acid of the type HOaS- NHR:

wherein R represents hydrogen, an acyl group or a lnonocycllc arylgroup, sa1 d dyes being soluble in concentrated sulphuric acid and inwater and dyeing viscose silk in even level shades.

In testimony whereof we alfix our signatures.

RAINALD BRIGHTMAN PERCY CHORLEY.

